Mask and manufacturing method thereof

ABSTRACT

A mask and a manufacturing method thereof are provided. The mask comprises a body and a film layer comprising an oleophobic material and covering the surface of the body, thereby the possibility of the organic coagulation adhering to the surface of the mask is effectively reduced, and the contamination of the mask by the organic solvent and other volatile organic in the photoresist during exposure is also reduced.

The application is a U.S. National Phase Entry of InternationalApplication No. PCT/CN2014/083407 filed on Jul. 31, 2014, designatingthe United States of America and claiming priority to Chinese PatentApplication No. 201310421535.1 filed on Sep. 16, 2013. The presentapplication claims priority to and the benefit of the above-identifiedapplications and the above-identified applications are incorporated byreference herein in their entirety.

TECHNICAL FIELD

Embodiments of the present invention relates to a mask and manufacturingmethod thereof.

BACKGROUND

In the known lithographic process, especially in the proximity exposurelithography process, due to the reaction heat or light excitation duringthe exposure process, as illustrated in FIG. 1a , an organic solvent 2etc. remaining in a photoresist 1 evaporates to a mask 3 and condensesas an organic coagulation 4 on the surface of the mask 3. The contactangle θ between the mask 3 and the organic coagulation 4 is generallyless than 90 degrees, as illustrated in FIG. 1b , so that the organiccoagulation has a greater infiltration capacity to the mask and it isnot easy for the organic coagulation to fall. The organic coagulationadhering to the surface of the mask will contaminate the surface of themask, seriously affecting the exposure accuracy. In addition, thefrequency for cleaning the mask will be increased due to thecontamination of the surface of the mask by the organic coagulation,which is not conducive to long-term continuous production.

At present, an organic coagulation processing apparatus is generallyinstalled in an exposed area, the apparatus can decompose the organiccoagulation coagulating on the surface of the mask, and then thedecomposed organic coagulation can be brought out of the exposurechamber by means of a gas system in the apparatus, thereby reducing thecontamination of the mask by the organic coagulation during the exposureprocess.

SUMMARY

Embodiments of the present invention provide a mask and manufacturingmethod thereof to reduce the contamination of the mask by the organicsolvent in the exposure process.

At least one embodiment of the present invention provides a maskcomprising a body, and a film layer which covers the surface of the bodyand comprises an oleophobic material.

For example, one embodiment of the present invention provides a mask inwhich a contact angle of an organic coagulation on the film layer isgreater than 150°.

For example, one embodiment of the present invention provides a mask inwhich the oleophobic material is located on the surface of the filmlayer.

For example, one embodiment of the present invention provides a mask inwhich the oleophobic material is a fluorine-containing material.

For example, one embodiment of the present invention provides a mask inwhich the fluorine-containing material is1H,1H,2H,2H-perfluorodecyltrichlorosilane.

For example, in order to uniformly coat1H,1H,2H,2H-perfluorodecyltrichlorosilane on the body, a mask providedby one embodiment of the present invention further comprises: acrosslinked layer between the body and the film layer.

One embodiment of the present invention provides a mask in which amaterial of the crosslinked layer is silicone fiber. For example, thediameter of the silicone fiber is from 20 nm to 60 nm.

One embodiment of the present invention provides a mask in which thefluorine-containing material is fluorinated silicon dioxidenanoparticles. For example, the diameter of each one of the fluorinatedsilicon dioxide nanoparticles is from 100 nm to 200 nm.

Another embodiment of the present invention provides a manufacturingmethod of mask, comprising: providing a body of the mask; forming a filmlayer comprising an oleophobic material and covering the surface of thebody on the body of the mask.

One embodiment of the present invention provides a manufacturing methodof mask, wherein the oleophobic material is1H,1H,2H,2H-perfluorodecyltrichlorosilane; the method comprising:forming a crosslinked layer on the body to cover the surface of thebody; forming a film layer comprising1H,1H,2H,2H-perfluorodecyltrichlorosilane and covering the surface ofthe crosslinked layer on the crosslinked layer.

One embodiment of the present invention provides a manufacturing methodof mask, wherein the oleophobic material is fluorinated silicon dioxidenanoparticles; the method comprising: homogeneously dispersing thefluorinated silicon dioxide nanoparticles in an organic solution;spin-coating the organic solution with dispersed fluorinated silicondioxide nanoparticles on the surface of the body.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to clearly illustrate the technical solution of the embodimentsof the invention, the drawings of the embodiments will be brieflydescribed in the following; it is obvious that the described drawingsare only related to some embodiments of the invention and thus are notlimitative of the invention.

FIG. 1 a is a schematic diagram showing a known mask contaminated by anorganic solvent in a photoresist during exposure;

FIG. 1b is a schematic diagram showing a contact angle of an organiccoagulation on the surface of the known mask;

FIGS. 2a and 2b are structurally schematic diagrams of a mask providedby an embodiment of the present invention, respectively;

FIG. 3a is a schematic diagram showing a contact angle of an organiccoagulation on the surface of the mask provided by an embodiment of thepresent invention;

FIG. 3b is a schematic diagram showing the principle of the maskprovided by embodiments of the present invention.

DETAILED DESCRIPTION

In order to make the objects, the technical details and the advantagesof the embodiments of the invention apparent, the technical solutions ofthe embodiments will be described in a clearly and fully understandableway in connection with the drawings related to the embodiments of theinvention. It is obvious that the described embodiments are just a partbut not all of the embodiments of the invention. Based on the describedembodiments herein, those skilled in the art can obtain otherembodiment(s) without any inventive work, which should be within thescope of the invention.

The shape, the thickness and size of respective film layer in thefigures do not reflect the true proportions of the mask, the purpose ofwhich is merely to schematically illustrate the present invention.

The inventors of the present invention have noticed that the way ofinstalling an organic coagulation processing apparatus in an exposurearea requires installing a new device; the structure is complicated andthe cost is high.

As shown in FIG. 2a , the mask provided by an embodiment of the presentinvention includes a body 01 and a film layer 02 comprising anoleophobic material, which covers the surface of the body 01 and canreduce the adhesion of the organic coagulation.

An embodiment of the present invention provides a mask, in which thebody 01 of the mask is covered with the film layer 02 comprising theoleophobic material. Since a contact angle φ of an organic coagulation04 on the surface of the film layer 02 is large, and the adhesion isweak, as shown in FIG. 3a , the possibility of the organic coagulationadhering to the surface of the mask can be effectively reduced, as shownin FIG. 3b , thereby reducing the contamination of the mask by theorganic solvent in the photoresist during exposure.

The mask provided by the embodiments of the present invention can beapplied in various forms. For example, the mask can be a chrome mask, adry mask or a gravure mask, etc., which is not limited here.Hereinafter, the mask provided by the embodiments of the presentinvention is described with the chromium mask as an example.

For example, one embodiment of the present invention provides a mask, inwhich the contact angle of the organic coagulation on the surface of thefilm layer is greater than 150°, achieving the ultra oleophobic effect.Under the action of the weight of the organic coagulation, theinfiltration capacity of the organic coagulation to the mask is smalldue to its large contact angle on the surface of the mask, and thus itis easy for the organic coagulation to fall from the surface of themask.

For example, one embodiment of the present invention provides a mask, inwhich the oleophobic material is present on the surface of the filmlayer.

For example, one embodiment of the present invention provides a mask, inwhich the oleophobic material can be a fluorine-containing material.

For example, one embodiment of the present invention provides a mask, inwhich the fluorine-containing material may be1H,1H,2H,2H-perfluorodecyltrichlorosilane or fluorinated silicon dioxidenanoparticles. Of course, the used oleophobic material can also be othermaterials that can achieve the technical solutions of the presentinvention, which are not limited here.

For example, in one embodiment, the fluorine-containing material is1H,1H,2H,2H-perfluorodecyltrichlorosilane. In order to uniformly coat1H,1H,2H,2H-perfluorodecyltrichlorosilane on the body, as shown in FIG.2b , a mask provided by one embodiment of the present invention canfurther comprise a crosslinked layer 03 between the body 01 and the filmlayer 02, which enables uniform distribution of1H,1H,2H,2H-perfluorodecyltrichlorosilane.

One embodiment of the present invention provides a mask, in which amaterial of the crosslinked layer 03 is silicone fiber. For example, thediameter of the silicone fiber is controlled in the range of 20 nm to 60nm. Of course, in order to uniformly coat1H,1H,2H,2H-perfluorodecyltrichlorosilane on the body, the material ofthe crosslinked layer 03 can also be other materials that can achievethe technical solutions of the present invention, which are not limitedhere.

For example, in one embodiment, the fluorine-containing material isfluorinated silicon dioxide nanoparticles, the diameter of each one ofthe fluorided silicon dioxide nanoparticles is for example from 100 nmto 200 nm.

Based on the same inventive concept, embodiments of the presentinvention also provide a manufacturing method of mask comprising:providing a body of the mask; forming a film layer comprising anoleophobic material on the body of the mask, wherein the film layercovers the surface of the body and can reduce the adhesion of theorganic coagulation.

The step of forming the film layer comprising the oleophobic material onthe body has been added in the manufacturing method of mask provided byembodiments of the present invention. Since the contact angle of theorganic coagulation on the surface of the film layer is large, and theadhesion is weak, the possibility of the organic coagulation adhering tothe surface of the mask can be effectively reduced, thereby reducing thecontamination of the mask by the organic solvent in the photoresistduring exposure.

One embodiment of the present invention provides a manufacturing methodof mask, wherein the oleophobic material can be1H,1H,2H,2H-perfluorodecyltrichlorosilane or fluorinated silicon dioxidenanoparticles, of course, it can also be other materials that canachieve the technical solutions of the present invention, which are notlimited here.

One embodiment of the present invention provides a manufacturing methodof mask, wherein the oleophobic material is1H,1H,2H,2H-perfluorodecyltrichlorosilane. Thereby, the examples offorming the film layer comprising the oleophobic material and coveringthe surface of the body on the body of the mask comprises: forming acrosslinked layer on the body to cover the surface of the body, whereinthe crosslinked layer enables the homogeneous distribution of the1H,1H,2H,2H-perfluorodecyltrichlorosilane to be formed on the surface ofthe cross-linked layer afterwards; forming a film layer comprising1H,1H,2H,2H-perfluorodecyltrichlorosilane on the crosslinked layer tocover the surface of the crosslinked layer.

Further, one embodiment of the present invention provides a mask, inwhich a material of the crosslinked layer is silicone fiber. Forexample, the diameter of the silicone fiber is controlled in the rangeof 20 nm to 60 nm. Of course, in order to uniformly coat1H,1H,2H,2H-perfluorodecyltrichlorosilane on the body, the material ofthe crosslinked layer can also be other materials that can achieve thetechnical solutions of the present invention, which are not limitedhere.

For example, in order to increase the contact surface between the bodyand the crosslinked layer, in the manufacturing method of mask providedby one embodiment of the present invention, before forming thecrosslinked layer covering the surface of the body, the surface of thebody can be etched using etching technology to increase the roughness ofthe surface of the body, so that the crosslinked layer can be formedmore easily on the body.

For example, one embodiment of the present invention provides amanufacturing method of a mask, wherein the oleophobic material isfluorinated silicon dioxide nanoparticle. Thus, one example of formingthe film layer comprising the oleophobic material and covering thesurface of the body on the body of the mask includes: homogeneouslydispersing the fluorinated silicon dioxide nanoparticles in an organicsolution; spin-coating the organic solution with the dispersedfluorinated silicon dioxide nanoparticles on the surface of the body.

Further, one embodiment of the present invention provides amanufacturing method of mask, wherein for example, the diameter of eachone of the fluorinated silicon dioxide nanoparticles is controlled inthe range of 100 nm-200 nm.

For example, one embodiment of the present invention provides amanufacturing method of mask, wherein the organic solution can be anisopropanol solution, of course, the organic solution also can be othersolutions that can achieve the technical solutions of the presentinvention, which are not limited here.

The manufacturing method of mask provided by embodiments of the presentinvention is described in detail below by way of two specific examples.

EXAMPLE 1

1H,1H,2H,2H-perfluorodecyltrichlorosilane is adopted as the oleophobicmaterial comprised in the film layer that covers the body of the mask.The manufacturing method of mask comprises the following steps:

S401: providing a body of the mask.

The body, for example, is a glass plate, a quartz plate or the like.

S402: etching the surface of the mask body using etching technique.

For example, the inductively coupled plasma (ICP) etching techniquePlasmaPro™ System 100 ICP180 can be used, and chlorine (Cl₂), oxygen(O₂) and helium (He) are used as the etching gas to etch the surface ofthe body so as to increase the roughness of the surface of the body. Forexample, a etching depth is generally controlled within 50 nm.

S403: forming a crosslinked layer of silicone fiber material on thebody.

For example, after being etched, the body can be immersed into a mixedsolution of methyltrichlorosilane and water, and a layer of crosslinkedsilicone nanofibers will grow on the surface of the body through thehydrolysis process of methyl trichlorosilane. For example, theconcentration of water is less than or equal to 200 ppm in the mixedsolution of methyltrichlorosilane and water. The hydrolysis rate ofmethyltrichlorosilane can be controlled, and further the diameter of thecrosslinked silicone nanofibers can be controlled by adjusting theconcentration of water in the mixed solution. Further, e.g., thediameter of each one of the crosslinked silicone nanofibers is generallycontrolled in the range of 20 nm-60 nm.

S404: activating the surface of the cross-linked layer of silicone fibermaterial using oxygen plasma.

For example, in one embodiment, under the condition that the pressure ofoxygen gas system is maintained at about 30 Pa and the Radio Frequency(RF) power is controlled in the range of 100 W-150 W, the crosslinkedlayer of silicone fiber material is treated for 5 min-10 min using RFplasma apparatus, and thus active hydroxyl groups are produced on thesurface of the crosslinked layer of silicone fiber material. In thisway, the roughness of the surface of the crosslinked layer of siliconefiber material is increased, which facilitates the succeeding formationof the oleophobic material on the surface of the crosslinked layer.

S405: anchoring 1H,1H,2H,2H-perfluorodecyltrichlorosilane on the surfaceof the crosslinked layer of silicone fiber material using moleculardeposition method, so as to form the film layer comprising theoleophobic material and covering the surface of the body.

For example, firstly, 1H,1H,2H,2H-perfluorodecyltrichlorosilane isdissolved in a toluene solution, then the cross-linked layer of siliconefiber material is immersed in this toluene solution,1H,1H,2H,2H-perfluorodecyltrichlorosilane is linked to the activehydroxyl groups on the surface of the crosslinked layer of siliconefiber material, thereby 1H,1H,2H,2H-perfluorodecyltrichlorosilane isanchored on the surface of the crosslinked layer of silicone fibermaterial, and the film layer containing the oleophobic material andcovering the surface of the body is formed.

For example, when the mask manufactured by the above method is exposed,the experiments show that the contact angle of the coagulation of xylene(a solvent commonly used in a negative photoresist) on the surface ofthe mask is generally greater than 150°, the roll angle is generallyless than 5°, and that the adhesion on the mask is also low. Thus, underthe action of the weight of the coagulation, it is easy for thecoagulation to fall from the surface of the mask surface. And it canalso be obtained through experiments that, the surface of the mask alsoshows good oleophobic property and low adhesivity for other organicsolvents such as hexadecane and mineral oil. In addition, the surface ofthe mask also has a good anti-UV irradiation ability, goodanti-reflective property, high transmittance (transmittance greater than90%) and chemical stability, which satisfies the requirements of thelithography process.

EXAMPLE 2

Fluorinated silicon dioxide nanoparticles are adopted as the oleophobicmaterial that covers the body of the mask. The manufacturing method ofthe mask comprises the following steps:

S501: manufacturing a body of the mask.

The body, for example, is a glass plate, a quartz plate or the like.

S502: homogeneously dispersing fluorinated silicon dioxide nanoparticlesin an isopropanol (Iso Propyl Alcohol, IPA) solution.

S503: spin-coating the isopropanol solution with the dispersedfluorinated silicon dioxide nanoparticles on the surface of the body ofthe mask, obtaining a film layer containing an oleophobic material andcovering the surface of the body.

For example, the fluorinated silicon dioxide nanoparticles used in stepS502 can be produced in the following manner:

Firstly, tetraethoxysilane is added to the isopropanol solution andstirred evenly;

Then, under intense stirring, ammonium hydroxide is added to the mixedsolution of tetraethoxysilane and isopropyl alcohol;

Thereafter, the mixed solution reflux for about 2 hours at a temperatureof about 60 degrees Celsius;

Finally, 1H,1H,2H,2H-perfluorodecyltrichlorosilane is added to the mixedsolution, the reaction is terminated, and fluorinated silicon dioxidenanoparticles are obtained. The diameter of each one of the fluorinatedsilicon dioxide nanoparticles is for example from 100 nm to 200 nm.

For example, when the mask manufactured by the above method is exposed,the experiments show that the contact angle of a coagulation of xylene(a solvent commonly used in negative photoresist) on the surface of themask is generally greater than 140°, the roll angle is generally lessthan 3°, and that the adhesion on the mask is also low. Thus, under theaction of the weight of coagulation, it is easy for the coagulation tofall from the surface of the mask. And it can also be obtained throughexperiments that, the surface of the mask also shows super-oleophobicproperty and low adhesivity for other organic solvents such as decalinand diesel oil.

Embodiments of the present invention provide a mask and a manufacturingmethod thereof, wherein the mask comprises a body, and a film layerwhich covers the surface of the body and comprises an oleophobicmaterial. Embodiments of the present invention provide a mask, whereinthe body of the mask is covered by a film layer comprising an oleophobicmaterial. Since the contact angle of the organic coagulation on thesurface of the film layer is large, and the adhesion is low, thepossibility of the organic coagulation adhering to the surface of themask can be effectively reduced, thereby reducing the contamination ofthe mask by the organic solvent in the photoresist during exposure.

Obviously, those skilled in the art may make various modifications andvariations of the present invention without departing from the spiritand scope of the invention. Thus, if such modifications and variationsof the present invention fall into the scope of the claims and thetechnical equivalents, the present invention is also intended to includethese changes and modifications.

The present application claims the benefits of the Chinese ApplicationNo. 201310421535.1 filed on Sep. 16, 2013, the entire disclosure ofwhich is incorporated herein by reference.

The invention claimed is:
 1. A mask, comprising: a body; a film layercomprising an oleophobic material and covering the surface of the body;and a cross-linked layer disposed between the body and the film layer,the cross-linked layer comprising silicone fiber.
 2. The mask accordingto claim 1, wherein a contact angle of an organic coagulation on thefilm layer is greater than 150°.
 3. The mask according to claim 1,wherein the oleophobic material is located on the surface of the filmlayer.
 4. The mask according to claim 1, wherein the oleophobic materialis a fluorine-containing material.
 5. The mask according to claim 4,wherein the fluorine-containing material is1H,1H,2H,2H-perfluorodecyltrichlorosilane.
 6. The mask according toclaim 1, wherein the diameter of the silicone fiber is from 20 nm to 60nm.
 7. The mask according to claim 4, wherein the fluorine-containingmaterial is fluorinated silicon dioxide nanoparticles, and the diameterof each one of the fluorinated silicon dioxide nanoparticles is from 100nm to 200 nm.
 8. The mask according to claim 2, wherein the oleophobicmaterial is located on the surface of the film layer.
 9. The maskaccording to claim 2, wherein the oleophobic material is afluorine-containing material.
 10. The mask according to claim 3, whereinthe oleophobic material is a fluorine-containing material.
 11. The maskaccording to claim 8, wherein the oleophobic material is afluorine-containing material.
 12. A manufacturing method of mask,comprising: providing a body of the mask; forming a cross-linked layercovering the surface of the body on the body of the mask; and forming afilm layer comprising an oleophobic material and covering the surface ofthe cross-linked layer.
 13. The manufacturing method according to claim12, wherein the oleophobic material is1H,1H,2H,2H-perfluorodecyltrichlorosilane.
 14. The manufacturing methodaccording to claim 12, further comprising: before forming thecross-linked layer covering the surface of the mask body on the body,etching the surface of the body using an etching technique.
 15. Themanufacturing method according to claim 12, wherein the oleophobicmaterial is fluorinated silicon dioxide nanoparticles; and wherein themethod further comprises: homogeneously dispersing the fluorinatedsilicon dioxide nanoparticles in an organic solution; and spin-coatingthe organic solution with dispersed fluorinated silicon dioxidenanoparticles on the surface of the body.